Azo compounds containing a triazolylthio group

ABSTRACT

AZO COMPOUNDS HAVING THE FORMULA   (A-N=N-B)-(S-T)N   WHERE A IS A PHENYL OR PHENYL OR PHENYLAZOPHENYL DISPERSE DYE DIAZO COMPONENT; B IS AN ANILINE) NAPHTHYLAMINO, TETRAHYDROQUINOLINE OR INDOLE DISPERSE DYE COUPLING COMPONENT, T IS A 1,2,4-TRIAZOL-3-YL RADICAL AND T IS 1, 2 OR 3 ARE USED IN DYEING CELLULOSE ACETATE POLYESTER AND POLYAMIDE FIBERS IN BRIGHT YELLOW TO BLUE SHADES WHICH ARE DEEP AND LEVEL AND EXCELLENT FASTNESS TO WASHING, CRACKING, LIGHT GAS AND SUBLIMATION.

United States Patent 4 1 3,816;392 'AZO'aCOMIOUNDSfiCDNTAINING ATRIAZQLYLTHIO GROUP 1 Max A. weaver and Clarence A. Coates, Jr.,Kingsport, Tenn., assig'noi's to Eastman Kodak Company, ...B0 1 ,N!Y- a,e No Drawing; Continuation-inpart of applications Ser. No.772,-846",No'"v-." 1,: 1968," which-is a continuation-inpart of Ser. No.784,215, Dec. 16, 1968, both now abandoned. This application Nov. 9,1971, Ser. No. 197,141 r A Int. Cl.*C09b 29/36, 31/14; D06p 1 I15 US.Cl. 260157- 25 Claims AB TR CT v01 IHED Azocompounds having the formula(A'N=N-' B (S )n where A'is a phenyl or phenyl,or phenylazophenyldisperse dye diazo componeu't;-, B is an aniline) naphthylamino,tetrahydroquinoline or indole disperse dye coupling component, T is a1,2,4-triazol-3-yl radical and T is 1, 2 or 3 are used in dyeingcellulose acetate polyester and polyar' nide fibers in bright yellow toblue shades which are deep and level. and excellent fastuess to washing,cracking, light gaslandsublimation f oline or indole disperse dyecoupling component;

vTis a l,2,4-triazo l-3 *y l radical; and ,fl-iS1,201' 3. The azocompounds ofthe inyentionnimpartbright yel- 1mm blue. shades tocellulose-acetate, polyester and poly.- arnide fibers, yarns andfabrics, novel azocompounds; ingeneral, exhibit improved properties,such as dyeability and fastness properties,;- when compared -toanalogouszazo somp ds whi h-do ot am a n t z y h gro p- The improveddyeability possessed by our novel compounds enable themjo produce,oncellulose acetate and polyamide fibers 'deep', level sha'deswhichincrease significantly inidepthas increasing-amounts of the dyecourpound are applied :to the fibers. The good dyeability of ourazocompounds also is manifested'by their excellent fastmess to washingand crocking. The novel a z o compounds 3 is an anil ine, ,l,2,3,4-tetrahydr oquin 3,816,392 Patented June 11., 1974 "ice alsoexhibit excellent fastness to light, gas, and sublimation. Although ournovel compounds, in general, are particularly useful for dying celluloseacetate and, especially, polyamide fibers, many exhibit excellentproperties on polyester fibers.

The diazo component of our novel compounds can be unsubstituted orsubstituted with groups well 'known in the art in addition to one ormore triazolylthio groups which also can be present on the diazocomponent. Examples of such groups include lower alkoxy, aryl, nitro,halogen, lower alkylthio, lower alkoxycarbonylalkylthio,

'cyclohexylthio, arylthio, lower aralkylthio, formyl, lower alkanoyl,lower alkoxycarbonyl, aroyl, lower alkanoylamino, aroylamino, cyano,lower alkylsulfonyl, arylsulfonyl, lower alkylsulfonamido,trifluoromethyl, sulfamoyl, lower alkylsulfamoyl, carbamoyl, loweralkylcarbamoyl, thiocyanato, etc. The alkanoyl groups can be substitutedwith substituents such as halogen, phenyl, cyano, lower alkoxy, loweralkylthio, lower alkylsulfonyl, etc. The alkylsulfonyl groups can alsobe substituted, for example, with cyano, hydroxy, halogen and the like.The alkoxycarbonyl groups can be substituted, for example, with hydroxyor cyano. As used herein to describe a group containing an alkyl moiety,lower designates a carbon content from 1 to about 4 carbon atoms.Examples of the alkyl and alkoxy groups which can be present on thediazo components include methyl, ethyl, isopropyl, propyl, butyl,methoxy, ethoxy, propoxy, butoxy, etc. Chlorine and bromine are typicalhalogen atoms. Methylsulfonyl, ethylsulfonyl, propylsulfonyl,butylsulfonyl, 2-cyanoethylsulfonyl, 2-hydroxyethylsulfonyl, acetyl,propionyl, butyryl, isobutyryl, 3-chloropropionyl, cyanoacetyl,methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, 2-cyanoethoxycarbonyl,Z-hydroxyethoxycarbonyl, etc. are examples of the alkylsulfonyl,alkanoyl, and alkoxycarbonyl groups which can be present on the groupsrepresented by A.

Acetamido, propionamido, methylsulfonamido, ethylsulfonamido, andbutylsulfonamido are typical alkanoylamino and alkylsulfonamidosubstituents which can be present on the diazo component.Dimethylsulfamoyl, ethylsulfamoyl, butylsulfamoyl, diethylcarbamoyl,propylcarbamoyl, dibutylcarbamoyl are examples of the alkylsulfamoyl andalkylcarbamoyl groups. The aryl groups which can be present on the diazocomponent including the aryl moiety of the arylthio, aralkylthio, aroyland arylsulfonyl groups are preferably monocyclic, carbocyclic aryl suchas phenyl and phenyl substituted, for example, with lower alkyl, e.g.tolyl; lower alkoxy, e.g. anisyl; halogen, e.g. chlorophenyl,bromophenyl; etc. 'Benzoyl, p-toloyl, p=chlorobenzoyl, pmitrobenzoyl,p-ethoxypheuylthio, p-chlorobenzylthio, benzamido, p'-tolylamino,p-tolylsulfonyl, p-ethoxyphenylsulfonyl, etc. are examples of thearyl-containing groups which canbe present on the groups representedbyA,

Illustrative of the phenylradicalswhich R can represent arez; -r ".1. 1,v a

2j.-.ch lorc 4-n ttbphe y I 4 9Pheny1M 2;chl iq-lrmethylsulfonyl,

, 2 et hoxycarbonyl l nitrophenyl,

2,6-dicyano-4-nitrophenyl, 4-methoxycarbonylphenyl,2-trifluoromethyl-4-nitrophenyl, 2,4-dicyanopl1enyl,2-bromo-6-cyano-4-nitrophenyl, 4-nitro-2-sulfamoylphenyl,2-nitro-4-(dimethyl)sulfamoylphenyl, 4-cyanophenyl,

4-methylsulfonyl phenyl, 4-trifluoromethylphenyl, 4-chlorophenyl4-ethylsulfamoylphenyl, 4-acetylphenyl, 4-ethylcarbamoylphenyl,2-carbamoyl-4-nitrophenyl, 2-methylsulfonyl-4 thiocyanphenyl,2,6-dichloro-4-nitrophenyl, 2-nitro-4-thiocyanatophenyl,2chloro-6-cyano-4-nitrophenyl, 2-cyano-4-nitrophenyl,2-chloro-4-cyanophenyl, 2-chloro4-ethoxycarbonylphenyl.

Examples of the phenylazophenyl radicals represented by A are:

4-phenylazophenyl,

4- 4'-methylphenylazo) phenyl,

4- 2,5 '-di-methylphenylazo) 3-methylphenyl,

4- (4'-acetamidophenylazo) -2,5-dimethoxyphenyl, 4- (3-benzamidophenylazo 3 chlorophenyl, etc.

Preferably, the phenyl diazo components of the monoazo compoundscontains not more than three substituents at the para and orthopositions.

One preferred group of the diazo components represented by A and whichdo not contain a triazolylthio group have the formula wherein R ishydrogen, halogen, cyano, formyl, lower alkanoyl, benzoyl, loweralkoxycarbonyl, lower alkylsulfonyl, sulfamoyl, lower alkylsulfamoyl,carbamoyl, lower alkylcarbamoyl, or trifluoromethyl;

R is halogen, cyano, lower alkylsulfonyl, lower formyl, lower alkanoyl,benzoyl, lower alkoxycarbonyl, sulfamoyl, lower alkylsulfamoyl,carbamoyl, lower alkylcarbarnoyl, trifluoromethyl, or nitro;

R is hydrogen, halogen, cyano or nitro; and

R, R and R are the same or diiferent and each is hy drogen, lower alkyl,lower alkoxy, or halogen and n is 1 or 2.

In addition to the substituents described hereinabove, the diazocomponents represented by A also can be substituted with one, two orthree triazolythio groups having the formula S-T. Preferably, .thetriazolylthio and other substituents on the phenyl diazo componentarepositioned at the ortho and/or para positions. 7

It is apparent that, in addition to being attached directly to a nuclearcarbon atom of the diazo components represented by A, the triazolythiogroup also can be attached to the diazo indirectly through a widevariety of bridging groups. Examples of such bridging groupsincludealkyl, alkoxy, alkylthio, alkanoyl, alkanoyloxy, alkanoylamino,alkoxycarbonyl, alkoxycarbonylamino, alkylsulfonyl, alkylsulfonamido,aryl, 'ar'ylthio; aryloxy and combinations of such groups, e.g.alkanoyloxyalkoxy. In general, any group capable of containing ahaloalkyl or haloaryl moiety, such as those set forth above, canfunction as the bridging group connecting the group ST to a nuclearcarbon atom of the carbocyclic diazo component.

A preferred group of the phenyl diazo components which are substitutedwith a triazolylthio group contain only one or two triazolylthio groupsor one or two triazolylthio groups and one or more substituents selectedfrom the group consisting of halogen, lower alkylsulfonyl, cyano, loweralkoxycarbonyl, sulfamoyl, lower alkylsulfomyl, carbamoyl, loweralkylcarbamoyl, trifluoromethyl, lower alkoxy, lower alkyl, formyl,lower alkanoyl, aroyl, aryloxysulfonyl, alkanoylamino, or'aryloxy.Preferably the nucleus of the phenyl diazo component is substituted withnot more than three substituents at the orthoand/or para-positions. a

A preferred group of the phenylazophenyl diazo components bearing atriazolylthio group have the formula wherein ring U can be unsubstitutedor substituted with any of the substituents described in the precedingparagraph and ring V can be unsubstituted or-substituted with one or twosubstituents selected from lower alkyl, lower alkoxy, halogen or atriazolylthio radical, provided that one of rings U and V bears at leastone triazolylthio.

The carboxylic nucleus of the aniline, tetrahydroquinoline and indolecoupling components can be substituted with a wide variety of well knowncoupler substituents. Alkyl, alkoxy, aryloxy,'alkylthio, arylthio,hydroxy, acylamido, etc., are typical of each coupler substituents. Thecarbon atoms of the heterocyclic moiety of the tetrahydroquinoline andindole couplers can be substituted with groups such as alkyl, alkoxy,halogen, alkanoyloxy, aryl, etc. The nitrogen atom of the aniline,tetrahydroquinoline, and indole couplers can be substituted with a widevariety of alkyl, substituted alkyl, cycloalkyl and aryl groups. Inaddition to the substituents mentioned above, the couplers representedby B also can be substituted with one or more triazolylthio groups. Thetriazolylthio group can be attached directly to a nuclear carbon atom ofthe coupler nucleus or it can be attached indirectly through a bridginggroup such as those mentioned hereinabove. Preferably, the triazolylthiogroup is attached, either indirectly or directly, to a nuclear carbonatom of the aniline or naphthylamine coupling component or to thecarbocyclic moiety of the tetrahydroquinoline coupling component. Thetriazolythio group also can be attached to the nitrogen atom of theaniline, naphthylamine, tetrahydroquinoline, and indole couplingcomponents through an alkyl group or through one of the bridging groupsset forth above which are attached to such an alkyl group, e.g. a2-(Z-triazolylthioacetoxy)ethyl group. Our novel azo compounds includecompounds in which both diazo component A and coupling component Bcontain one. or more triazolylthio groups. However, the presence oftriazolylthio groups on both A and B 'does not result in any substantialbenefits but only increases the cost of the compounds. The compounds ofthe invention which contain a triazolylthio-substituted diazo componentpreferably contain a phenyl diazo component in which one or twotriazolylthio groups are attached'directly to one orboth of the ortho'carbon atoms (relative to the 'azo group) of the phenyl diazo group.Thesecompounds conformto the formula i (11 -(T'.'-s );;A i-r=N B whereinA is described "in' the preceding sentence, B and T are definedhereinabove and n is one or two. As mentioned'above, in compounds (H), Bpreferably is devoid of the triazolylthio group. 1/

wherein A is a phenyl or phenylazophenyl diazo component, preferablydevoid of triazolylthio group, B is the coupling component described inthe preceding sentence, T is a triazolyl radical and n is one or two.

A generally preferred group of couplers have the for wherein X is loweralkyl or lower alkoxy; m is 0, 1 or 2; R is hydrogen, a nalkyl radical,allyl, cyclohexyl, a phenyl radical, or the group R -ST, R is a loweralkylene radical; T is a 1,2,4-triazol-3-yl radical; Q, Q and Q each ishydrogenor lower alkyl; Y is an acyl radical; Z is hydrogen, X, or-NH--Y; R is one of the alkyl radicals which R .can represent; R is analkyl radical; R is alkanoyl, alkoxycarbonyl or alkylsulfonyl containingup to six atoms; R is hydrogen or an alkyl radical; and R .is loweralkyl or aryl.

Methyl, ethyl, butyl, methoxy, ethoxy, chlorine and bromine arerepresentative of the substituents which X can represent. Preferably,when m is 2 the substituents, which can be the same as different,represented by X are positioned para to one another. It is alsopreferred that Q and Q each is hydrogen, or methyl and Q is methylor,when Q and Q each is hydrogen, Q also can be lower alkyl.

The alkyl-radicals represented, by R", R and R can be unsubstituted orsubstituted 'straightor branch-chain alkyl. The number of carbon atomspresent in such alkyl radicals generally is not critical but isdetermined by costzproperty considerations. For example, although a'carbon atom content of eight or more is feasible, a carbon content offour or less usually is preferred. Representative examples. of suchalkyl radicals include methyl, ethyl, 'propyl, isopropyl, butyl,isobutyl, etc., hexyl, 2-

ethylhexyl, octyl and lower alkyl substituted, for example, withhydroxy, e.g. Z-hydroxyethyl, 2,3-dihydroxypropyl; lower alkoxy, e.g.Z-methoxyethyl; cyano, e.g. Z-cyanoethyl; lower cyanoalkoxyalkyl, e.g.2-cyauoethoxyethyl; lower alkanoyloxy, e.g. acetoxyethyl; loweralkoxycarbonyl, e.g. 2-ethoxycarbonylethyl; lower alkanoylamino, e.g.Z-acetamidoethyl, 3-propionamidopropyl; carbamoyl, e.g.2-carbamoylethyl; lower alkylcarbamoyl, e.g. ethylcarbamoylethyl, 3dimethylcarbamoylpropyl; phenylcarbamoyloxy, e.g.2-phenylcarbamoyloxyethyl; lower alkylsulfonyl, e.g.Z-methylsulfonylethyl, lower alkoxycarbonyloxy, e.g. CH OCOOCH CHdicarboximido, e.g. 3-phthalimidopropyl, 3-glutarimidopropyl;Z-succinimidoethyl; cyclohexyl, e.g. cyclohexylmethyl, e.g. benzyl,Z-phenylethyl; aryloxy, e.g. 2-phenoxyethyl; lower alkylsulfonamido,e.g. Z-methylsulfonamidoethyl; pyrrolidinono, e.g.2-(2-pyrrolidinono)ethyl; piperidono)- propyl; phthalimidino, e.g.2-phthalimidinoethyl; etc. Cyclohexyl and lower alkylcyclohexyl aretypical of the cyclohexyl groups which R can represent. The aryl moietyof the aralkyl and aryloxy groups which R can represent preferably ismonocyclic aryl such as phenyl and phenyl substituted, for example, withlower alkyl, lower alkoxy, halogen, hydroxy, lower alkoxycarbonyl,cyano, etc. Benzyl, phenylethyl, p-ethylbenzyl, p-methoxybenzyl,mbromobenzyl, o,p-dichlorobenzyl, p-methoxycarbonylbenzyl,p-hydroxybenzyl and rn-cyanobenzyl are typical aralkyl groupsrepresented by R".

R' and R also can represent joined alkylene groups optionallyinterrupted by an oxygen, sulfur or nitrogen atom or by a sulfonylgroup. When R and R each is such a joined alkylene group,

can be piperidino, morpholino, thiomorpholino, piperizino, or4-thiomorpholino-1,l-dioxide group.

The alkylene radicals represented by R can be straightor branch-chain,unsubstituted or substituted alkylene containing up to about 4 carbonatoms. Chlorine, bromine, lower alkoxy and lower alkanoyloxy are typicalsubstitutents which can be present on the alkylene chain. Examples ofthe alkylene radicals represented by R include ethylene, propylene,isopropylene, butylene, isobutylene, Z-chloropropylene,2-hydroxypropylene.

The acyl groups represented by Y can be formyl, lower alkanoyl, aroyl,cyclohexylcarbonyl, lower alkoxycarbonyl, aryloxycarbonyl, loweralkylsulfonyl, arylsulfonyl, carbamoyl, lower alkylcarbaoyl,arylcarbomoyl, furoyl, etc. The alkanoyl, alkoxycarbonyl, andalkylsulfonyl groups can be substituted as described above in thedefinition of A. Acetyl, propionyl, butyryl, cyanoacetyl, chloroacetyl,phenylacetyl, methoxyacetyl,, methylthioacetyl, methylsulfonylacetyl,methoxycarbonyl, propoxycarbonyl, butoxycarbonyl, methylsulfonyl,ethylsulfonyl, propylsulfonyl, butylsulfonyl, 2-cyanoethylsulfonyl,2-methoxyethylsulfonyl, and 2-chloroethylsulfonyl, are examples of thealkanoyl, alkoxycarbonyl, and alkylsulfonyl groups which Y canrepresent. The aryl group of the aroyl, aryloxycarbonyl, arylsulfonyl,and arylcarbamoyl group is preferably monocyclic, carboxylic aryl suchas unsubstituted phenyl and phenyl substituted with, for example, loweralkyl, lower alkoxy, halogen, etc. Tolyl, anisyl, pbromophenyl, ando,p-dichlorophenyl are typical of such aryl groups. Dimethylcarbamoyl,ethylcarbamoyl, propylacyloxyalkyl, alkoxycarbonylalkyl,dialkylaminoalkyl, alkanoyl, aroyl, dicarboximidoalkyl,vinylsulfonylethyl, alkylsulfonyl, arylsulfonyl, etc. Examples of thesesubstitutes appear in the above description of A and R". A preferredgroup of triazolyl radicals have the general formula N-N-R" .4315

ljjh 11L t l Although the triazolyl groups are described herein and inthe claims, both generically and structurally, as the 1H form, the 2Hand 4H forms are within the scope of the invention. When R is other thanhydrogen, T represents 1,2, or 3 isomeric, but different groups andthus, an azo compound containing an N-substituted triazolyl group canactually be a mixture of 2 or 3 compounds. It is to be understood thatthe description of such azo compounds appearing herein covers the 3isomeric forms thereof.

Particularly good dyeings of cellulose acetate and/or polyamide textilematerials are obtained by applying to those materials a compound havingthe general formula I UL l RS R15 wherein A is a group having theformula R is hydrogen, lower alkyl, or phenyl; and

Q, Q Q and Q are the same or difierent and each is hydrogen or methyl.

Dyeing having particularly good fastness properties on celluloseacetate, polyamide and/or polyester textile materials, such as excellentfastness to light and resistance to sublimation and polyester fibers,are obtained by ap plying thereto a compound having the formula B1 I lIL N=N N-B.!-S n A N NH-Y wherein A is a group having the formulawherein R is hydrogen, chlorine, bromine, cyano, lower alkanoyl, loweralkoxycarbonyl, lower alkylsulfonyl, or trifluoromethyl;

R is nitro, lower alkylsulfonyl, or thiocyanato;

R is hydrogen, cyano, or nitro;

Y is lower alkanoxyl, benzoyl, lower alkoxycarbonyl, loweralkylsulfonyl, or lower alkylcarbamoyl;

X is hydrogen methoxy, or ethoxy;

R is lower alkyl, lower cyanoalkyl, lower hydroxyalkyl, loweralkoxy-lower-alkyl, lower alkanoyloxy-oweralkyl; or benzyl;

R is ethylene or propylene;

R is hydrogen, methyl, ethyl, cyanoethyl, or benzyl; and

R is hydrogen, methyl or phenyl.

Another group of our novel azo compounds which are particularlypreferred, because of their excellent proper ties on polyamide fibers,have the formula wherein R is hydrogen, cyano, lower alkylsulfonyl,lower alkoxy carbonyl, halogen, sulfanoyl, lower alkylsulfanoyl orbenzoyl;

R is hydrogen or -ST; T is a group having the formula in which R ishydrogen, lower alkyl, cyanoethyl or hydroxyethyl; and R is hydrogen,lower alkyl or phenyl; and

B is a group having the formula wherein Y is lower alkanoyl;

X is hydrogen or methyl R is lower alkyl; lower alkyl substituted withhydroxy, lower alkanoyloxy, benzoyloxy, lower alkoxycarbonyl,

19 lower alkoxycarbonyloxy, lower alkanoylamino, loweralkoxycarbonylamino, benzamido, carbonyl, lower, alkylcarbonoyl, loweralkylsulfonamido;eyclohexyl, 1qwer alkox'y, lowjer alkylsulfonyl;orwheiiX is methys hy-I droge'n;- V p 15 Q R is cyclohexyl; lower alkylsubstitutedwitli'hydroxy or lower alkanoyloxy; or preferablyunsubstituted lower alkyl- I R is lower alkyl or lower alkyl substitutedwith by; droxy, lower alkanoyloxy, benzoyloxy, lower alkoxycarbonyl,lower alkanoylamino, lower alkoxycarbonylamino, benzamido, carbamoyl,.lower alkylcarbanoyl, lower alkylsulfonamido, cyclohexyl, lower alkoxyor lower alkylsulfonyl;

Z is hydrogen, methyl,

Q is methyl; 1 a

Q and Q each is hydrogen or methyl;

R is hydrogen, lower alkyl or lower alkyl substituted with cyano, loweralkanoylamino, lower alkoxycarbonylamino, benzamido, carbanoyl, loweralkylcarbanoyl, lower alkylsulfonamido, succinimide or glutarimido; and

R is methyl or phenyl.

or lower alkanoylamino;

Still another group of compounds which exhibit excellent properties whenapplied to polyamide fibers have the formulas It. X

' in 1 1110 -R -Si ,l-R"

and

wherein R1 is hydrogen, chlorine, bromine, cyano or lower alkylsulfonyl;

R is lower alkylsulfonyl, cyano, lower alkoxycarbonyl, chlorine orbromine;

R is hydrogen, chlorine or bromine;

-X is hydrogen or, when R is hydrogen, X is methyl;

Z is hydrogen, methyl or lower alkanoylamino;

R in the first formula, is hydrogen, lower alkyl or lower alkylsubstituted with loweralkanoylamino or carbamoyl, and in-the secondformula R is hydrogen or lower alkyl; y g I R is ethylene or propylene;r

R is lower alkyl, cyclohexyl or benzyl; 1

R is alkylene having one to six; carbon atoms; R is hydrogen, loweralkyl, cyanoethylor hydroxyethyl;and v,

R is hydrogen, lower alkyl or phenyl.

The novel compounds of the invention can be prepared by procedures wellknown in the artrFor example, an amine having the formula A.NH can bediazotized and the resulting diazonium salt coupled with a compoundhaving the formula 1 to obtaintthelicompounds of the "invention whichcontain a coupler substituted'with a-triazolylthio group. The conplersH-B-S-T can be obtained by reactingtheanalogous halide'havingihe formula.H:.A' Cl with a mercaptotriazole" according-to known techniques. The'mercaptotriazoles, having the formula HS-T, which are substituted atthe 1-position are prepared by reacting a mercaptotriazole with (1) anacylating agent such as an alkylsulfonyl halide, an arylsulfonylchloride, an alkanoic anhydride or acid halide, or an aroyl halide, (2)an alkylating. agent such as a dialkylsulfate, an alkyl arylsulfonate, atrialkyl phosphate, an aralkyl halide or an alkyl halide, (3) anactivated vinyl compound such as acrylonitrile or divinylsulfone, or (4)an epoxide such as ethylene oxide, propylene oxide, epichlorohydrin,styrene oxide. Methanesulfonyl chloride, p-tolylsulfonyl chloride,acetic anhydride, propionic anhydride, acetyl chloride, benzoylchloride, dimethyl sulfate, diethyl sulfate, ethyl p-toluenesulfonate,triethyl phosphate, benzyl chloride, ethyl bromide, 1,2-dibromoethane,and l-bromo-B-chloropropane are examples of the acylating and alkylatingagents useful in preparing the l-substituted mercaptotriazoles. The 3-mercaptotriazoles which are substituted at the 5-position are preparedaccording to known procedures.

The following compounds are typical of the couplers that are preparedaccording to the procedures described above:

M.P., C. 3-[2-(N ethylanilino)ethylthio]-1H-1,2,4-tria- The novel azocompounds containing a triazolylthiosubstituted diazo component can beprepared by diazotizing an amine having the formula TSANH and couplingthe resulting diazonian salt with a coupler having the formula HB. Theamines of formula are prepared according to the following reactionsequence:

, HS- l H2 ClAN0 TS-AN0;' T-S-A-NH,

A second method which can be employed in preparing the azo compoundshaving a triazolylthio-substituted diazo component consists of reactingahalo-substituted azo compound having the formula Cl--AN=N-B with amercaptotriazole. As a class of compounds, the interme-' diate azocompounds are well-known in the art. The described displacement reactiongenerally is carried out in a solvent such as dimethylformamideor'N-methylpyrrolidinone in the presence of a copper catalyst such ascuprous bromide. 1

Although the preceding description of the means for preparing our novelcompounds has been, for the sake of simplicity, directedto thepreparation of azo compounds containing one triazolylthio, it isapparent that those pro- EXAMPLE, iii- I p-Chloroaniline is dissolved"r'nl.

and 3 ml. conc. HCl. .The solution is cooled to.,05. C. and then asolution of (.72 g.) NaNO in 2 ml. of water is added below 5 C. for 1hr.,"and then the solutionis added to a chilled solution of3-[2-(n-ethyl-m-toluidino) ethylthio]-lH-1,2,4-triazole (2.6 g.)dissolved in 50 ml. of 1:5 acid (1 part propionic acid:5 parts aceticacid). The coupling is kept at -5 C. and neutralized with ammoniumacetate until it is neutral to Congo red paper. After coupling for 1hr., the mixture is drowned into water. The product is collected byfiltration, washed with water, and air dried. The azo compound obtainedproduces bright, fast, yellow shades on cellulose acetate and polyamidefibers. It has the formula:

EXAMPLE 2 ('5 2H5 Ncrncms This compound imparts bright scarlet shades tocellulose acetate and polyamide fibers.

EXAMPLE 3 Sodium nitrite (0.72 g.) is added portionwise to 5 ml. ofconcentrated sulfuric acid. The solution is cooled and ml. of 1:5 acidis added below C. The mixture is cooled further and 2.5g.2,4-bis(methylsulfonyl)aniline is added followed by 10 ml. of 1:5 acid,all below 5 C. After stirring for 2 hours at 0-5" C., the diazoniumsolution is added to a chilled solution of 3.16 g. 3-[2-(2,2,4,7-tetramethyl 1,2,3,4 tetrahydroquinolino)ethylthio]-lH- 1,2,4-triazole in50 ml. of 1:5 acid below 5 C. The reaction is kept cold and :ammoniumacetate, added until the coupling mixture is neutral to Congo red testpaper. After allowing to, couple ,forpl ,hour at about} C., the reactionmixture is drowned in" water. The product is collected by filti ation,washed withwater', and d ried in air. The azo compoundnobtained givesbright red dyeings having excellent fastnes's' properties on poly'amidefibers and has the structure:

CHaS O A rd: of 0 g. of the azo-compound prepared in 3;'I.()'g.'potassium carbonate, 2.5 ml. of dimethylfor'ma'mi'de, and 0.3"g.iodoethane is heated with stirring at 5 lfitlfi; C. f or 3 0 minutesThereaction mixture is d; ,ne'd 200ml. water. The product is collected byfiltration, 'washed with water, and dried in air. The azo compoundobtained produces bright redshades on .polyamide fibers and has theformula:

e la) EXAMPLE 5 To 5 ml. conc. H is added 0.72 g. of NaNO with stirring.This solution is'cooled 'and 10 ml. 1:5 acid is added below 10 C. Thisis stirred and 2.08 g. Z-cyano- 4,6-dinitroaniline is added followed by10 ml. additional 1:5 acid, all at 0-5 C. The diazotization is stirredat 05 C. for 3 hr. and then added to a chilled solution of 3.05 g.3-[2-(m-acetamido-n-ethylanilino)ethylthio]-lH-1,2,4- triazole dissolvedin ml. of 1:5 acid-"The coupling is kept cold (below 5 C.) and bufferedwith ammonium acetate until neutral toiCongo Red paper. After allowingto couple for 2 hr., the azo product is drowned in water, collected byfiltration, washed :with water and dried in air. The product,4-(2-cyano-4,6-dinitrophenylazo) 3 acetamido Nethyl-N,2-(1H-l,2,4-triazol-3-ylthio)ethylaniline, produces bright blueshades on polyester fibers.

EXAMPLE, 6

EXAMPLE 7 Sodium nitrite (0.72 g.) is added portionwise to 5 ml. ofconcentrated sulfuric acid. The solution is cooled and 10 ml. of 1:5acid is added below 15 C. The mixture is cooled further and 2.5 g.2,4-bis (methylsulfonyDaniline is added followed by 10 ml. of 1:5 acid,all below 5f C. After stirring for 2 hrs. at 0-5 C., the diazoniumsolution is added to a chilled solution (below 5 C.) of 4.45 g. 3[2-(m=benzamido-N,fi-cyanomethylanilino)ethylthio]- lH-1,2,4-triazole in100 ml. of 15% sulfuric acid below 5 C. The reaction is-kept cold andammonium acetate is added until the coupling mixture is neutral to CongoRed test paper. After allowing to couple for 1 hr. at about 5 C.,the'reaction mixture is drowned in water. The prodnet is collectedbyfiltration, washed with water, and dried in air. The product, 4-(2,4dimethylsulfonylphenylazo)-3- benzamido N,B-cyanoethyl-,B1-p-cyanoethyl-1H-1,2,4- triazol-3-ylthio)ethylaniline, "gives reddyeings of excellent fastness on polyester fibers. Substituting 1.47 g.of S-amino- 3-methylthio 1,2,4 thiadiazole for the thiadiazole employedin the preceding example. This azo dye imparts red shades to polyesterfibers.

EXAMPLE 8 H A mixtureof l-bromp-Z-nitrobenzene 10.1 g.), 3-mercapto-l'(H)-1,2,4 triazole (7.5 g.), potassium carbonate (7.0 g.),N,N-dimethylformamide (50.0 ml.), and a trace of cuprous bromide isheated at -l30 C. for 2 hr. The reaction mixture is drowned into Waterand allowed to stand overnight. An insoluble by-product is collected byfiltration and the filtrate is acidified with conc.

HCl. The pale yellow product, collected by filtration and recrystallizedfrom ethanol, meltsat 142-144 C. This 3- (o nitiophenylthio) ,2,;4'-tfiazo1e is hydrogenated in ethanol'at 75 C. and at" 1 500'pTsi.hydrogen pressure in the presence of a platinum catalyst. The amine,3-(0- aminophenylthio)-l (H)-l,2,4-triazole, crystallizes as thereaction mixture is cooled and melts at 174175 C. Anal.Calcd. for C H NS: C, 50.0; H, 4.2; N, 29.1.

Found: C, 49.6; H, 4.2; N, 29.3.

3-(o-Aminophenythio)-1(H)-l,2,4-triazole (1.92 g., .01 mole) isdissolved in a mixture of water (10 ml.) and concentrated HCl (3 ml.).To this is added a solution of sodium nitrite (0.72 g.) in water (3 ml.)below 5 C. After being stirred at -5" C. for 30 min. the diazoniumsolution is addedilto a chilled solution of N-(2-acetamidethyD-N-ethyl-mhacetamidoaniline (.01 m.) dissolved in 40 ml. of 1:5 a cid (1part propionic acid: parts acetic acid). The coupling mixture isbuffered by adding ammonium acetateLfAfter standing for about 1.,hr.below 20 C., the coupling mixture is drowned: intofiwater. The stickyazo product 3- acetamidoeNfi-acetamidoethyl-N-ethyl-4- (2 1 (H): .4 tiazol-3+y1thi z1pheny azo) is washed y decantation and dried iri'aii".-After being recrystallized from methanol the product melts at 188-190 C.The azo compound obtained produces yellow shades on nylon and celluloseacetate fibers and exhibits excellent fatness to light and washing.

'-' EXAMPLE 9 A mixture of 2-acetamido-2'-bromo-4'-cyano-4-(diethylamino),azobenZene. (0.41 g.), 3-mercapto-1(H)-1,2,4-triazole(0.2 g.),-potassium carbonate (0.2 g.), N,N-dimethylformamide (5.0 mli),and}. trace of cuprous bromide is heated and stirred at':1 25? Ci.for0.5 hr. and then drowned intofwater; Acetic Yacid isadded'Igi; furtherprecipitate the product The product, i 2acetahiido-4'-cyano-4-(diethylamino)-2'-(1H-l,2,4-triazol-3ylthio)azobenzene; is col lected by filtration, washed with Water, anddried in air. It dyes nylon bright pink shades and exhibits excellentlight fastness and wash fastness.

EXAMPLE 10 Amixture of 2acetamido-2'-bromo-4-cyano-4-cyclohexylamino-S-rnethylaaobenzene (0.5g.), B-mercapto-IH- 1,2,4t1iazo'le (0.2 g.), potassium carbonate (0.2g.), N,N- dimethylformamide (l0 l 1, and a trace of cuprous bromideisheated-at'13 0f ff or fihr. and then drowned intowater. The mixtu'i-i isacidified with acetic acid and the'azo product isjcollected; byfiltration, washed with water, and dried '-'i nj air. The product,2-acetamido-4'- cyano 4-jcyclohexylamino-5-me'thyl-2'-(lH-l,2,4-triazol3-ylthioazobenzene), produces a bright pink shade and exhibitsjexcellentlight @fastness, sublimation fastness, and wash fastness on polyamidefibers.

a 2 EX MPLE 1 A mixture of Z-acetamido-Ayanno-2,6'-dibromo-4-diethylamino azobenzene (0.98 g.),;3-mercapto-l(H)-1,2,4- triazole' (0.6 g.), potassium carbonate (0.4 g.),N,N-dimethylformamide (1.5 ml ,and -a trace of cuprous bro;midei'sheatei at 125-130 V iofS hraand then'drowned into' water. Theproduc cbllectediby filtration, washed eproduct; 2.-acetarnido-4"- Tmethyl-'2',- 6f-di(1H)-1,2,4 iylthio) aiobenieiieadyespolyamide fibersin bright pink shades 'afl'd has excellent light'fastness and washfastness XAMPLE 12 A mixture of 2-acetamino-2'-bromo-4-(diethylamino)-4'-m'ethylsulfonyl azobenzene w gfi, 3-mercapto-l(H)-' 1,2,4-triazole(0.4 g.), potassium carbonate (0.2 g.), N,N-

dimethylformamide (20.0 ml.), and a trace of cuprous bromide is heatedat C. for 2 hrs. with stirring. The product is isolated as isillustrated in previous examples. The azo compound obtained, 2acetamido-4-(diethylamino) 4'methylsulfonyl)-2'-(lH)-1,2,4-triazol-3-ylthio)azobenzene, produces abright red shade on polyamide fibers and has excellent fastnessproperties.

EXAMPLE 13 A mixture of 2-acetamido-2-bromo-4-(diethylamino)- 4(ethoxycarbonyl)azobenzene (1.0 g.), 3-mercapto-1 (H)-1,2,4-triazole(0.4 g.), potassium carbonate (0.2 g.), N,N-dimethylformamide (15 ml.),and a trace of cuprous bromide is heated and stirred at 135 C. for 3hrs. The product, isolated as described previously, is Z-acetamido- 4(diethylamino) 4'ethoxycarbonyl-2'-(1H-1,2,4-triazol-3-ylthio)azobenzene. This dyeproduces very bright scarlet shades on polyamide tricot fabrics andcarpets.

EXAMPLE 14 A mixture of7-acetamido-6-(2-bromo-4-methylsulfonylphenylazo) N ethyl 2,2,4trimethyl 1,2,3,4 tetrahydroquinoline (1.04 g.),3-mercapto-1(H)-1,2,4-triazole (0.4 g.), potassium carbonate (0.2 g.)N,N-dimethylformamide (20 ml.), and a trace of cuprous bromide is heatedand stirred at -140 C. for 1 hr. The product is isolated as illustratedpreviously. The product has the structure:

CH3 N CH; S O N=N CH3 ENE N CH3):

produces bright red shades on polyamide tricot and has outstanding washfastness.

EXAMPLE 15 3 2 Rfl (RN) to in which R R and R each is hydrogen or asubstituent. The color given for each of the examples of Table I refersto the shade which are azo compound disclosed in each example produceson cellulose acetate and poly amide fibers. 'InTable I, thelH-1,2,4-tria Zol-3-ylthio group is designated ST.

0 5000+" $5050 0 56520052 1 ETz z mmfi 6 3m m moamo m o mo ommz 3:5 z zm-u 05 55050505 5050 5 50505055050 5 00052 355.52.. 55050505 50505005500 250500052 2 .5 2 51. 55 7 7 $5050 205050652 2 2 5 1 s 5 $505055050002 5050 5 00052 A 52 00 56 v 8 5 P25050 52005050 500052 v 3880 550 205050 20500052- H 3 000" 0 $5050 5 0 5 00052 7 2E r E 5. $5050 5 0500052 1 E 02 E0.- N0 05 $5050 505050 E= 0m50-n$ 55 55050 H 56 Em 55050205050 05 55050 5 01 505050 5 0 05 $5050 .7 50 65 $5050 5 0 5 5050505056 5 $5050 505050 5 5 50250055050 502500 5 $5050 523525050 5 550505050505050 :0 55050000525050 5 0 05 0050005250550 52005050 50 3 5 552? N5 5500005050 205050 50 i fi fim moi 5 50 50 8505955050 5 0 50 3 2 2. 520 561 QMEEo 8m50500075059 2 5050 55 50 0050 -13 55 3 050 5506 5050 56 55 5002595 5050 5 050 .3820 56 5500005050+5050 500005050 65 5 205050550505 0 5 5 5 952 500 650505050 5 55050 5 0 0 $5050 55 65 5 5055050 1 6555050 5005050 0 55050 5 0 22 550505050 5 0 85 $5050 50 :0 55050505005050 5 5050 5 0 0 m 55050 5 0 6 002500 802500 5 0.05050 505050 6- 3=200050+ 5 .255 $5050 $5050 5 3 2 00055 @550 m mo mo 50 No 1 11 c mm 55535050 5 0 5 -4 2 000505 HHPHN 65 '$5050 205050 5 2 2 02 -HH 5 5 55050 50 65 4 3 65 2 $555 $5050 $5050 5 5 5 550 5 35 $5050 5 0 50 -3=2 -02 v20.m 5 E85 5050 5 0 5 fi oziqa 8 828m 5.5500 5 0 5 2 2 073 2 5 5 55050 5 05 -3 5 205 -2 05 5.05050 55 50 0 20 55065 N 2 5 0 5 0 em 2 5 55050205050 50 2 5 $55 925050 5 0 5 1 35350 5 255805 2 0 2m :5 v 4 n 50 5650mQO w moooo mofio 5H0 n 9 wooooo mo mo Eo mooomz 2m EO HOEO EH6 E m owofioamol Eo mo oomz hm monvoo uHUA mo-Ooovmo mo m U mOOOmZ I: I- I L temu A NOVHHOOEOANOVMOEO M 0 "M mZ ou mfiofiovmofio Ee 500053 "i mc mo mm6 nmooomz gnwsa m kog zqu w Manor? .ENOI HH O m0 OOHZ -fimgn w o d vm WE51 E O E0252 E sn m 0 -2m EM MNOI mmo EOOOMZAN a nn mb ozgow nmflol m umooowz H EQ WEQ N m5 M0 oomza Engn m omao m E fi m o 5000 HHO NOEO m omooomnz I c E mfi mo 500056 2a idol E6 mooomz u -w fl 31m E m u 50 00m JE ZQ Q 5m RH .551 E6 $600M? wnfismme oza omsw nvm wmw 6Q JHNOI mmuol"HMO OOmHZ A s m oz mgmO w m m H E m u mooomcfim J E BWQS wfiqioz El "EDmooomz --$=2E Ew 5Z+Eooon; mmm 561 56 500cm? $8295 20 2 2.1 mmw @Qmmflol m u 5000M? E iwio vi moqm ED ED "HO O OM24 AESQ O z mqm mw :mGlEo E0005? 2 5 EO MOEO HH O 5000 ow w w fl m SWZOONHHONWOII RENO].nmOOUmZwm t bmm moQUE/3650 nmooomz Em H mmo 5000M? -QEEQWQSwE mma 5225E6 :m O mooomz 49235 N mw 25m E E5 mooomz Q fim $2 m. mmw 6mm H m omOOOmZ QcEn J N mmm 523$ ED um o moo OmZ -acwsn waqm m 6mm EO "m0 OOmZ Iga w a Q 6mm m u E O mo oOmZ Eaa wkmo 60M #101 al 22. 56 E6 6Q 55 E5mooomz EE Q 55m m o E5 mo oomz fimw woo moe 6Q ED 55 "mo Quiz- -afia woomz 6Q 55 5O oomz Efinn w fimo $2.55 $10 E D m0 QUEZ-m QEQ Q QMU 20 d$205 E G o "MO oumzm QE Q 102 6Q 551 m5 fiooomz ifigmw qm ovzooa 6Q E 56"mo oowza -i fim fim omz owv gm a fimimo mo o moiozo m- E6 56 mo oomzrill. m8 $2.5m HM m o JAG-WHO oOmZ -EQ Q EQ L m .5 m Hfio mo mooomzaafifim e :5 E E O mooomz EEVE ZHQ oo wqo a 6Q 55 H 10 "m0 Quiz E= m m 0056 m 6Q ZOSHOEO m o mooomza .l. 0 -mDOOmZ-HHO-HmU BHHNOI. mooomz t wow45 H E EO G o mo oomz -ihngm m wzo 6Q E m u "mo ooflz -QEE A WE SGama1... 8 6Q E E5 fiooomz i nnx w m oa $20 2: H200 m :3 ham v 4 23 Thephenyl diazo components A set forth in Table I also can be combined witha wide variety of tetrahydroquinoline, naphthylamine and indole dispersedye coupling components.

Azo compounds containing any of the phenyl diazo Since the compounds ofthe invention are substantially water-insoluble, i.e. free of Watersolubilizing groups, they can be applied to cellulose acetate, polyamideand polyester textile fibers, yarns and fabrics according to knowndisperse dyeing techniques. If desired, dyeing assistants,

5 components A set forth in Table I and a naphthylamine, i.e. carriers,such as butyl benzoate, can be employed. tetrahydroquinoline or indoledisperse dye coupling com- The following example illustrates one methodby which ponents are synthesized according to the procedures dethe novelcompounds of the invention can be applied to scribed hereinabove.Typical of such azo compounds are cellulose acetate fibers. those setforth in the examples constituting Table II. 10 EXA MPLE 335 The azocompounds of Table II conform to the general f l A N=N B, Th 1H 1,2,4-t1-3- 1 group 0.1 g. of the compound described in Example 3 is disisrepresented by ST and THQ represents a 1,2,3,4-teti-asolved in 10 cc. of2-rnethoxyethanol. A small amount hydroquinol-6-yl group. (3-5 cc.) of a3% sodium lignin sulfonate aqueous solu- TABLE II Example A B Color 256.4-CHaS0z-pheny1 2,2,4,7-l3et1a-CHs-l-CHzCHzST-THQ Orange2,7-di-CH3-1-CH2CH Do. 2,4-di-CHnsOz-phenyl- 2,7-di-CH31-CHzCHzSTTHQPink. l-CHzCHzST-THQ Do. -do.-

2,2,4,7-tetra-CH3-1-(CHi)3-(5-CHi-ST)THQ.- Do. do-2,2,4-tri-CH3-7-Cl-l-OH2CH2(5OHaST)-THQ Do 4Cl-phenyl2,2,4,7-tetra-CH3-1-CH2CHzST-THQ Yellow 4-Br-phenyl do Do.

2-01-4-CH3S02-phelly 2-CH(CHa)2-7-OH -1-CH CH2(1-OH2CHzOH-ST)THQScarlet. 2-C1-4-C4HoSO2-ph0nyl 2-OH3-7-OCzH5-1-(CH2);ST-THQ Do. 4-(4'-N2-05 r-N 1-(CH2)iST-THQ Red. 4-CHO- henyl2,2,4,7-tetra-CH3-1-OHiCHiO-CHiCH NST) Orange i-cim OC-pheriy2,2,4,7-tetra-CHa-l-CH2CH2STTHQ.. Do. 2 CH3S O2-4-OH3C o-2,2,4,7-tetra-CH3-l-OH2OHz(1-C zH5-ST Red. 2-CH3S O2-4-CF=-pheny1 doRed. i-NOz-phemrl ,2,4,7-t8tI3-CHa-l-CHzCHzST-TH Red.

4-CN-phenyl Orange.

4-CN-2-CH3SOTD11QDY1- ed. 2,4,6-tri-CN-pl1enyl 2,2,4,7-tetra-CH-LCHzCHzST-THQ Violet. 2-Cl-4-CH3S0z-pheny12,2,4,7-t6tl8-CHz-l-CHzCHzOOCHrST-THQ.- Orange.

2,2,4,7-tetra-CH -1-CH2CHzNHCOCH ST-THQ- Do. 2-CH -7-ST-1-CzH -THQ Do.2-CH3-7-NHC O CHs-1-CH2CH2O CHzCHzST-THQ- D0. d 7-CHa-3-ST-1-OH2CoH5-THQDo. 4-CN-plienyl 2,2,4-tri-OH3-8-ST-1-CH2CH OH)CHzST-THQ, Do.4-CH3SOi-2-ST-phenyl- 2,2,4,7-tetra-CH -l-CzH -T Q Red. do2,2,4-tIl-CH3-1-C2H5-TH Red. (10 2,2,4-tI'i-CHs-1-OH2CH2C NHz-THQ Red.do--- 2,7-di-CHr1-CH2CHaCONHz-THQ Red. 285 --do 2,7-di-c Ha-l-CHQCHziNHCo o Hg-THQ, Red. 286- .-do- 2-CH3-7-NHC o CHg-l-C HiCHzNHC 0 CHg-THQ-Red. 2s7 -do 2-CHi-7-NHCOOH -1-CzH -THQ Red. 288 4-CZH OOC-2-ST-phenyI2-OH3-7-NHCOCHg-l-CzH -THQ Red. 289-- -do-7-NHCOCH3-2,2,4-tri-CH3l-CzH5-THQ Red. 290... do---7-NHCOCHa2,2,4-tri-CHa-l-CHzCHaOH-THQ Red. 291 4-CN-2-ST-phenyl 7-NHCOCH2,2,4-tri-CH;-1-CHQCH:OHTHQ.. Pink. 292 do-NHCOCHa-2,2,4-triCH3-1-C2H5THQ, Do. 293 do7-NHCOOH3-2,ZA-tIi-CHz-l-CHzCHqOOCCH3-THQ- Do. 294 4-CN-2,6-di-ST-pheny17-NHOOCH3-2-CH3-l-CgH5-THQ Violet 295 do 7-NHcocH3-2-cH(oHon-oiHPTH Do.7-NHCOCH3-2-CH3-1-CH2CH1CONHr-THQ- Pink. 7-NHCOCH3-2CH3-1-CH2CH2CONHPTHQ- Do. 7-NHCOCHs-2-CHa-1-CzH5-THQ. Do.7-NHCOCaHii-2-CH -1-CgH5-THQ D0. 7-NHCOCiH -2CH3-1-C H THQ Do.7-NHCOCH2OH-2-CH3-1-C2H5TH Do. 302 7-NHCOCH3-2-CHa-1-CiH5-THQ. Do. 303--do--. 7-NHCOCH3'2-CH3'1-CH2CH2CON Do. 304.- 4-Cl-2,6-di-ST-phenyl7-NHCOOH3-..CH3-1-CzH5-THQ Red. 305 4-Br-2,o-di-eT- iion 17-NHOOOHs-2-CHa-1-C2H5-THQ Red. 3 5-SOgN(CH3)2-2-ST-pheny17-NHCOCH3-2-CH3-1-C1H5-THQ Red. 307..-- 4-czHssofl-2-sT-phenyl 2,-di'CH3-1-CH2CH2OCIHa-THQ, Red. 308 -do 2,7-di-CH3-1-CHzCHiS OzCH3-THQRed. 309 .--do 2,7-di-CH3-1-cH2CHflS'I IHQ, Red. am do2,7-di-CH3-1-CHgCHqN(CH )SOCH -THQ Red. d 2,7-di-CHa-1-CH2COH5THQ. Bed.

Z-CoH -1-CH1CHrST-3-ind0ly1 Yellow 2-CH -1-CHiCHaST-3-indolyl Do. 2-0oH-l-CHaCHr-ST-S-iudolyl..-.. Do. 4-CiH OOC-2-ST-phenyl. 1-CH3-2-CuH-3-ind01yl Do.

2-Cl-4-CH S0; -pheny1--. l-CHgCHgNHCOCH3-2-CoH -3-indolyl Do.2-ST-phenyl 2-CiH5-3-ind01yl Do.

4-CH SO -2-ST-phenyl 2 CH 1 CH OH NCOClEhcH CH CO-li-lndolyl Do.

4-CN-2,6-diST-phenyl 2-COH5-1-CHfloHlooNfiraindolyl Do.

4-ciH5o0c-2,6-di-sT- hon i i-omd-coHi-a-indoi i 4-Cl 2,6-di-ST-phenyl 04-ON-phenyl 4(2-. SCH:CHiNH)1-naphthyl do 4-(C2H5-i[3-TSOH2CH(OH)CH:]N)2-Cl-4-CH SOi-phenyl. 4-(2-TSCHiCHzNH)-1-naphth do4-(2-TSOHzCONHCH:CHzNH-)1-I1aphthyl C1-4-CzH5OOC-phel14-(2-TSCHiCONHOHiCHgNH-)-l-naphthyl o 4-(2-TSCHzCH;NH)1-naphthyl Red.

4-CoH5NH-1-naphthyl Do.

4-HO CH:CH(OH) CHiNH-l-naphthyL Do.

o 4-OiH5NH-1-naphthy1 Do. 4-cN-2,6-di-s'rheii i4-(CHahCHCHiNH-l-naphthyl Do. o 4-CiHiiNH-l-naphthyl'imine Do.

tion is added, with stirring, and then the volume of the bath is broughtto 300 cc. with Water. 10 g. of a textile fabric made of partiallyhydrolyzed, cellulose acetate fibers (Estron fibers) is placed in thebath, worked for 10 minutes without heat, and then the bath is slowlybrought to 80 C. and the dyeing is continued for 1 hour. The dyed fabricis removed from the dyebath and scoured for 20 minutes at 80 C. in asolution containing 1 g./l. neutral soap and 1 g./l. sodium carbonate.The fabric is then rinsed and dried.

The dyeing procedure described above can be employed in the applicationof the novel azo compounds to polyamide textile materials except thatthe dyeing is carried out at the boil rather than at 80 C. In additionto dyeing partially hydrolyzed cellulose acetate, the azo compounds ofthe invention can also be used to dye unhydrolyzed cellulose acetatetextile materials. Examples of the polyamide textile materials that canbe dyed with the novel azo compounds are those consisting of nylon 66,made by the polymerization of adipic acid and hexamethylenediamine,nylon 6, prepared from epsilon-aminocaproic acid lactam, and nylon 8.

The compounds of the invention can be applied to polyester by knowndisperse dyeing techniques employing carriers, surfactants, dispersingagents, etc. Dyeing can be conducted at atmospheric or superatmosphericpressures. The following example illustrates a carrier dyeing procedurefor applying the azo compounds of the invention to dye polyester textilematerials.

EXAMPLE 336 The azo compound (0.1 g.) of Example is dissolved in cc. ofZ-methoxyethanol. A small amount (3-5 cc.) of a 3% sodium ligninsulfonate aqueous solution is added, with stirring, and then the volumeof the bath is brought to 300 cc. with water. 3 cc. of an anionicsolvent carrier (Tanavol) is added to the bath and 10 grams of a textilefabric made of poly(ethyleneterephthalate) fibers is placed in the bathand worked 10 minutes without heat. The dyeing is carried out the boilfor one hour. The dyed fabric is removed from the dyebath and scouredfor 20 minutes at 80 C. in a solution containing 1 g./l. neutral soapand l g./l. sodium carbonate. The fabric is then rinsed, dried in anoven at 250 F. and heat set (for the removal of residual carrier) for 5minutes at 350 C.

The compounds of the invention can also be applied to polyester textilematerials by the heat fixation technique described in US. Pat. 2,663,612and in the American Dyestutf Reporter, 42, 1 (1953). The followingprocedure describes how the azo compounds of the invention can beapplied to polyester materials by the heat fixation technique.

EXAMPLE 337 A mixture of 500 mg. of the compound of Example 3, 150 mg.of a sodium lignosulfonate dispersing agent (Marasperse N), 150 mg. of apartially desulfonated sodium lignosulfonate (Marasperse CB), 0.5 m1.glycerin, and 1.0 ml. of water is ground in a micro-size container (anaccessory for a l-quart size Szegvari Attritor) for approximately 3.5hours. Enough Ma-inch stainless steel balls are added to provide maximumgrinding. When the grinding is complete, the entire contents are pouredinto a beaker and 100 ml. of water are used to wash the remaining dyepaste from the micro-container. The dye paste is then heated slowly to65 C. With continuous stirring. A thickener and penetrating mixture isprepared by mixing 1 ml. of a complex diaryl sulfonate surfactant(compound 8-8), 3 ml. of a 3% solution of a sodiumN-methyl-N-oleoyltaurate (Igepon T-Sl), 8 ml. of a 25% solution ofnatural gums (Superclear 80 N), and suflicient water to bring the volumeto 100 ml. The thickener and penetrating mixture is added to the dyepaste, the volume 26 is adjusted to 200 ml. and the mixture is agitatedfor 15 minutes. The dye mixture is then filtered through foldedcheesecloth to remove the stainless steel balls and it then is added tothe reservoir of a Butterworth padder where it is heated to about 45--60C.

10 g. of a fabric of poly(ethylene terephthalate) fibers and 10 g. of afabric of 65/35 spun poly(ethylene terephthalate)/cotton fibers are sewntogether, end-to-end, and padded for 5 minutes of continuous cyclingthrough the dye mixture and between three rubber squeeze rollers of thepadder. Dye mixture pick-up is about 60% based on the weight of thefabrics.

The padded fabrics are then dried at 200 F. and then heat-fixed for 2minutes at 415 F. in a forced air oven. The dyed fabrics are scoured for20 minutes at 65-70 C. in a solution containing 0.2% sodiumhydrosulfite, 0.2% sodium carbonate and 1.7% of a 3% solution of sodiumN-methyl-N-oleoyltaurate and then dried. The dyed fabrics possessexcellent brightness and exhibit outstanding fastness to light andsublimation when tested according to the procedures described in the1966 edition of the Technical Manual of the American Association ofTextile Chemists and Colorists.

The heat fixation dyeing procedure described above can be varied by thesubstitution of other dispersing agents, surfactants, suspending agents,thickeners, etc. The temperature and time of the heat-fixation step canalso be varied.

Polymeric linear polyester materials of the terephthalate sold under thetrademarks Kodel, Dacron and Terylene are illustrative of the lineararomatic polyester textile materials that can be dyed with the compoundsof our invention. Examples of linear polyester textile materials thatcan be dyed with the compounds of the invention are those prepared fromethylene glycol and dimethylterephthalate or from cyclohexanedimethanoland dimethylterephthalate. Polyesters prepared fromcyclohexanedimethanol and dimethylterephthalate are more particularlydescribed in US. Pat. 2,901,446. Poly(ethylene terephthalate) polyesterEfibers are described, for example, in US. Pat. 2,465,319. The polymericlinear polyester materials disclosed in US. Pats. 2,945,010, 2,957,745and 2,989,363, for example, can be dyed. The linear aromatic polyestermaterials specifically named have a melting point of at least 200 C. Thepoly(ethylene terephthalate) fibers which are dyed with the compounds ofthe invention are manufactured from a melt of a polymer having aninherent viscosity of at least 0.35 and preferably, about 0.6. Theinherent viscosity of the poly(1,4-cyclohexylenedimethyleneterephthalate) polymer is also at least 0.35. These intrinsicviscosities are measured at 25 C. using 0.25 g. polymer per ml. of asolvent consisting of 60% phenol and 40% tetrachloroethane. Thepolyester fabrics, yarns, fibers and filaments that are dyed with thenovel azo compounds can also contain minor amounts of other additivessuch as brighteners, pigments, delusterants, inhibitors, stabilizers,etc.

This invention has been described in detail with particular reference tocertain preferred embodiments thereof, but it will be understood thatvariations and modifications can be effected within the spirit and scopeof the invention.

We claim:

1. A compound having the formula 27 wherein A is a group having theformula I O O O G-. w-o oor o o-N=N-o o 0+0 0:. L on t,

wherein R is hydrogen, chlorine, bromine, cyano, formyl, lower alkanoyl,benzoyl, lower alkoxycarbonyl, lower alkylsulfonyl, sulfamoyl, loweralkylsulfamoyl, carbamoyl, lower alkylcarbamoyl or trifiuoromethyl;

R is chlorine, bromine, cyano, lower alkylsulfonyl, lower formyl, loweralkanoyl, benzoyl, lower alkoxycarbonyl, sulfamoyl, loweralkylsulfamoyl, carbamoyl, lower alkylcarbamoyl, trifluoromethyl, ornitro;

R is hydrogen, chlorine, bromine, cyano or nitro;

and

R R and R are the same or dilferent and each is hydrogen, lower alkyl,lower alkoxy, chlorine or bromine and n is l or 2;

X is lower alkyl or lower alkoxy and m is O, 1 or 2;

R is hydrogen; lower alkyl; lower alkyl substituted with hydroxy, loweralkoxy, cyano, lower alkanoyloxy, lower alkoxycarbonyl, loweralkanoylamino, carbamoyl, lower alkylcarbamoyl, phenylcarbamoyloxy,lower alkylsulfonyl, lower alkoXycarbonyloxy, succinimido, glutarimido,phthalimido, phenyl, phenoxy, lower alkylsulfonamido, 2- pyrrolidinono,2-piperid0no, or 2-phthalimidino; cyclohexyl; phenyl; or phenylsubstituted with lower alkyl, lower alkoxy, chlorine or bromine;

R is lower alkylene;

T is a group having the formula l' o o-1w wherein R is hydrogen; loweralkyl; lower alkyl substituted with cyano, hydroxy, halogen, loweralkoxy, carbamoyl, lower alkanoyloxy or phenyl; or vinylsulfonylethyl;and R is hydrogen, lower alkyl, phenyl or phenyl substituted with loweralkyl, lower alkoxy, chlorine or bromine. 2. A compound having theformula 'R is hydrogen, chlorine, bromine, cyano, formyl, loweralkanoyl, benzoyl, lower alkoxycarbonyl, lower alkylsulfonyl, sulfamoyl,lower alkylsulfamoyl, carbamoyl, lower alkylcarbamoyl ortrifluoromethyl;

R is chlorine, bromine, cyano, lower alkylsulfonyl,

formyl, lower alkanoyl, benzoyl, lower alkoxycarbonyl, sulfamoyl, loweralkylsulfamoyl, carbamoyl, lower alkylcarbamoyl, trifluoromethyl, ornitro;

R is hydrogen, chlorine, bromine, cyano or nitro;

and

R R and R are the same or diflferent and each is hydrogen, lower alkyl,lower alkoxy, chlorine or bromine and n is 1 or 2;

Y is formyl, lower alkanoyl; lower alkanoyl substituted with chlorine,bromine, cyano, lower alkoxy, hydroxy, lower al kylsulfonyl, or phenyl;benzoyl; benzoyl substituted with lower alkyl, lower alkoxy, chlorine orbromine; cyclohexylcarbonyl; lower alkoxycarbonyl; lower alkoxycarbonylsubstituted with hydroxy or cyano; phenoxycarbonyl; phenoxycarbonylsubstituted with lower alkyl, lower alkoxy, chlorine or bromine; loweralkylsulfonyl; lower alkylsulfonyl substituted with cyano, hydroxy,chlorine or bromine; phenylsulfonyl; phenylsulfonyl substituted withlower alkyl, lower alkoxy, chlorine or bromine; carbamoyl; loweralkylcarbamoyl; di-lower alkylcarbamoyl; phenylcarbamoyl;phenylcarbamoyl substituted with lower alkyl, lower alkoxy, chlorine orbromine; or furoyl;

a X is hydrogen, lower alkyl, or lower alkoxy;

R is hydrogen; lower alkyl; lower alkyl substituted with hydroxy, loweralkoxy, cyano, lower cyanoalkoxy, lower alkanoyloxy, loweralkoxycarbonyl, lower alkanoylamino, carbamoyl, lower al kylcarbamoyl,phenylcarbamoyloxy, lower alkylsulfonyl, lower alkoxycarbonyl, loweralkoxycarbonyloxy, lower alkylsulfonamido, phthalimido, glutarimido,succinimido, phenoxy, pyrrolidinono, piperidino, or phthalimidino;cyclohexyl; lower alkylcyclohexyl; phenyl; phenyl substituted with loweralkyl, lower alkoxy, hydroxy, or nitro; aralkyl in which the alkylmoiety contains 1 or 2 carbon atoms and the aryl moiety is phenyl orphenyl substituted with lower alkyl, lower alkoxy, hydroxy, cyano, orlower alkoxycarbonyl; or the group R SR R is lower alkylene; and

T is a group having the formula wherein R is hydrogen; lower alkyl;lower alkyl substituted with cyano, hydroxy, chlorine, bromine, loweralkoxy, carbamoyl, lower alkanoyloxy or phenyl; or vinylsulfonylethyl;and R is hydrogen, lower alkyl phenyl or phenyl substituted with loweralkyl, lower alkoxy, chlorine or bromine. 3. A compound according toclaim 1 having the formula wherein R is hydrogen, chlorine, bromine,cyano, lower alkanoyl,

lower alkoxycarbonyl, or lower alkylsulfonyl;

R is chlorine, bromine, cyano, lower alkylsulfonyl, loweralkoxycarbonyl, or lower alkanoyl;

R is hydrogen, chlorine, bromine or cyano;

Q is hydrogen, methyl, or chlorine;

R is lower alkyl or lower alkyl substituted with hydroxy,

lower alkoxy, or cyano;

R is ethylene or propylene;

R is hydrogen, lower alkyl, cyanoethyl, or hydroxyethyl; and

R is hydrogen, lower alkyl, or phenyl.

4. A compound according to claim 3 wherein R is hydrogen, chlorine,bromine, or lower alkylsulfonyl;

R is chlorine, bromine, lower alkoxycarbonyl, or lower alkylsulfonyl;

R is hydrogen;

Q is hydrogen or methyl;

R is lower alkyl, 2-hydroxyethyl or Z-cyanoethyl;

R is ethylene; and

X and Y each is hydrogen.

5. A compound according to claim 1 having the formula NNH $2 0330 OCQ-N:Q-rrcmcm-s N I OH:

6. A compound according to claim 1 having the formula N--NH 02H;

7. A compound according to claim 1 having the formula N-NH C2115cmsoQrr: QI mmCHr-sl J in (III-I;

8. A compound according to claim 2 wherein A is a group having theformula s .4 Rr-. E-

N-N-R 14 wherein R is hydrogen, lower alkyl, phenyl, or phenylsubstituted with lower alkyl, lower alkoxy, chlorine, or bromine;

R is hydrogen; lower alkyl; lower alkyl substituted with cyano, hydroxy,chlorine, bromine, lower alkoxy, carbamoyl, lower alkanoyloxy, loweralkoxycarbonyl, lower dialkylamino, succinimido, glutarimido,phthalimido, or phenyl; cyclohexyl; or lower alkanoyl.

9. A compound according to claim 2 having the formula wherein R ishydrogen, chlorine, bromine, cyano, lower alkanoyl,

lower alkoxycarbonyl, lower alkylsulfonyl or trifluoromethyl;

R is nitro, lower alkylsulfonyl, or thiocyanato;

R is hydrogen, cyano, or nitro;

Y is lower alkanoyl;

X is hydrogen, methoxy or ethoxy;

R is lower alkyl;

R is ethylene or propylene;

R is hydrogen, methyl, ethyl, cyanoethyl or benzyl; and

R is hydrogen, methyl, or phenyl.

10. A compound according to claim 9 wherein R is hydrogen, chlorine orbromine; R is nitro;

R is hydrogen;

Y is acetyl;

X is hydrogen;

R is ethyl; and

R is ethylene.

11. A compound according to claim 9 wherein R is hydrogen, chlorine,bromine or methylsulfonyl; R is methylsulfonyl; R is hydrogen; Y isacetyl; X is hydrogen; R' is ethyl; and R is ethylene.

12. A compound according to claim 9 wherein R and R each is nitro; R iscyano; Y is acetyl; X is hydrogen; R is ethyl; and R is ethylene.

13. A compound according to claim 9 wherein R and R each is nitro;

R is chlorine, bromine or cyano; Y is acetyl;

X is methoxy or ethoxy;

R is ethyl; and

R is ethylene.

14. A compound having the formula wherein A is phenyl substituted at theortho-position, para-position, or orthoand para-positions with not morethan two substituents selected from the group consisting of chlorine,bromine, lower alkylsulfonyl, cyano, lower alkoxycarbonyl, sulfamoyl,lower alkylsulfamoyl, carbamoyl, lower alkylcarbamoyl, trifluoromethyl,lower alkoxy, lower alkyl, formyl, lower alkanoyl, aryloxysulfonyl,lower alkanoylamino, or aryloxy; T is a group having the formula1;I--N--R x:

in which R is hydrogen, lower alkyl, cyanoethyl or hydroxyethyl;

R is hydrogen, lower alkyl, or phenyl; and

n is one or two, the group T--S being attached to phenyl group A at theortho position(s);

Z is hydrogen, lower alkyl, lower alkoxy, chlorine, bromine, or thegroup NHY in which Y is lower alkanoyl, lower alkoxycarbonyl, benzoyl,or lower alkylsulfonyl;

X is hydrogen, lower alkyl, or lower alkoxy;

R is hydrogen; lower alkyl; or lower alkyl substituted with hydroxy,lower alkanoyloxy, lower alkoxycarbonyl, lower alkoxycarbonyloxy, NHY,cyclohexyl, lower alkoxy, lower alkylsulfonyl, or benzyl; and

R is lower alkyl; lower alkyl substituted with hydroxy or loweralkanoyloxy; or cyclohexyl;

in which each aryl group is phenyl or phenyl substituted with loweralkyl or lower alkoxy.

15. A compound according to claim 14 having the formula wherein R" ishydrogen, cyano, lower alkylsulfonyl, lower alkoxycarbonyl, chlorine,bromine, sulfamoyl, or lower alkylsulfamoyl;

R is hydrogen, chlorine or S-T;

T is a group having the formula in which R is hydrogen, lower alkyl,cyanoethyl or hydroxyethyl and R is hydrogen, lower alkyl, or phenyl;

Z is hydrogen, methyl, lower alkanoylamino or lower alkoxycarbonylamino;

X is hydrogen or methyl;

R is lower alkyl; lower alkyl substituted with hydroxy, lower alkoxy,lower alkanoyloxy, benzoyloxy, lower alkoxycarbonyl, loweralkoxycarbonyloxy, lower alkanoylamino, lower alkoxycarbonylamino,benzamido, carbamoyl, lower alkylcarbamoyl, cyclohexyl; or, when X ismethyl, R' is hydrogen; and

R is lower alkyl, lower hydroxyalkyl, lower alkanoyloxylower alkyl orcyclohexyl.

16. A compound according to claim 15 wherein R is hydrogen or S-T;

R and R each is hydrogen;

Z is lower alkanoylamino;

R is lower alkyl, lower alkanoylaminoethyl, cyanoethyl, carbamoylethyl,acetoxyethyl, or lower alkoxy, lower alkyl; and

R is lower alkyl or, when X is methyl, R is hydrogen.

32 17. A compound according to claim 16 having the formula N-NH CHaS O18. A compound according to claim 16 having the formula NHC OCH:

19. A compound according to claim 16 having the formula NNH NCQM MHMNHCOCH:

20. A compound according to claim 16 having the formula 21. A compoundaccording to claim 16 having the formula R is lower alkylsulfonyl,cyano, lower alkoxycarbonyl,

chlorine or bromine;

R is hydrogen, chlorine or bromine;

X is hydrogen or, when R is hydrogen, X is methyl;

R is hydrogen, lower alkyl or lower alkyl substituted with loweralkanoylamino or carbamoyl;

R is lower alkyl, cyclohexyl or benzyl;

R is alkylene having one to six carbon atoms;

R is hydrogen, lower alkyl, cyanoethyl or hydroxyethyl; and

R is hydrogen, lower alkyl or phenyl.

33 23. A compound according to claim 22 wherein R is hydrogen, chlorine,bromine or lower alkylsulfonyl;

R is chlorine, bromine, lower alkoxycarbonyl, or lower alkylsulfonyl;

R is hydrogen;

R is hydrogen or lower alkyl;

R is lower alkyl;

R is CH and R and R each is hydrogen.

24. A compound having the formula l -N-R 14 s E R" wherein R ishydrogen, chlorine, bromine, cyano, or lower alkoxycarbonyl;

R is lower alkylsulfonyl, cyano, lower alkoxycarbonyl,

chlorine or bromine;

R is hydrogen, chlorine or bromine;

X is hydrogen or, when R is hydrogen, X is methyl;

Z is hydrogen, methyl or lower alkanoylamino;

R is hydrogen or lower alkyl;

R is ethylene or propylene;

34 R is alkylene having one to six carbon atoms; R is hydrogen, loweralkyl, cyanoethyl or hydroxyethyl; and R is hydrogen, lower alkyl orphenyl.

25. A compound according to claim 24 wherein R is hydrogen, chlorine,bromine or lower alkylsulfonyl;

R is chlorine, bromine, lower alkoxycarbonyl, or lower alkylsulfonyl;

R is hydrogen;

Z is methyl;

R is CH and R and R each is hydrogen.

References Cited UNITED STATES PATENTS 8-41 B, 41 C, 260--154, 155, 165,308R Po-mso I UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIONPatent No, 3,816,392 D ed June 1]., Inventor)w Max A. Weayer,ClaIQElEQ/l. Coates, Jr.

It is certified that error appears in theabove-identificd patent andthat said Letters Patent are hereby correctcdhs shown below:

[ Co1umn 27, (Claim 1) lines 40-44, delete the formula therein andinsert l UQQ Column 27, (Claim 2), lines 63-69, delete the formulastherein and insert Column 28, (Claim 2), line 52, after "lower alkyl"insert a comma Column 29, (Claim 8), line 69, after "bromine;", insert-and-.

Signed and sealed this 8th day of October 1974,

( SEAL) Attest:

MCCOY M. GIBSON JR. C. MARSHALL DANN Arresting Officer Commissioner ofPatents TEC 10261

